Engineering Failure Analysis 39 (2014) 181–187

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Engineering Failure Analysis

journal homepage: www.elsevier.com/locate/engfailanal

Failure of pyrolysis coils coated with anit-coking film

in an ethylene cracking plant q
A. Goswami a,⇑, S. Kumar b
a
Department of Materials Engineering, Indian Institute of Science, Bangalore, Karnataka 560012, India
b
BG Exploration and Production India Limited, BG House, Lake Boulevard, Hiranandani Business Park, Powai, Mumbai - 400 076, India

a r t i c l e i n f o a b s t r a c t

Article history: This paper presents a specific kind of failure in ethylene cracking coils coated with anti-
Received 8 October 2013 coking film. It investigates a case in which the coils made of 35Cr 45Ni high temperature
Received in revised form 22 November 2013 alloy failed within two years of operation. The damage occurred due to heavy oxidation
Accepted 25 January 2014
in localized regions of the coil resulting in the formation of blisters, which eventually failed
Available online 7 February 2014
by cracking. The mechanism involved was determined by studying the oxidized samples
under a scanning electron microscope with an energy dispersive system and is attributed
Keywords:
to the presence of rare earth metals in the anti-coking film and inherent casting defects in
Anti-coking film
Rare earth elements
the base alloy. The cerium present in the anti-coking film diffused preferentially to a defect
Oxidation site in the parent alloy thereby resulting in its segregation which further led to
embrittlement.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction

Ethylene production in a petrochemical plant is carried out in a cracking furnace. These furnaces comprise of radiant coil
assemblies in which a pre heated mixture of hydrocarbons and steam is cracked at high temperatures of around 950–1150 °C
and at moderate pressure of 2–3 bars [1]. Such conditions demand the use of high metallurgy alloys which can demonstrate
excellent mechanical and physical properties at elevated temperatures. To fulfill this requirement the furnace coils are usu-
ally made of the Fe–Cr–Ni alloy system. These alloys exhibit excellent properties in terms of oxidation resistance, carburi-
zation resistance, high temperature creep and thermal expansion.
Further to this, many significant improvements have been made to reduce the damage in the furnace coils by reducing the
extent of carburization and oxidation. One of the ways that has been implemented worldwide in the last few years is by the
use of specially coated coils [2].
These coils are internally coated with a thin and adherent anti-coking film which is made up of composites with metallic
and ceramic constituents along with the presence of rare earths (RE) like yttrium, zirconium and cerium [3,4]. The rare earths
present in these coatings improve oxidation resistance and the low concentration of nickel, iron and other metals in the coat-
ing (which act as substrate for the formation of filamentous coke) enhances the carburization resistance of the furnace coils
[5–8]. Thus these anti-coking films serve a dual purpose.

q
This document is a collaborative effort.
⇑ Corresponding author. Tel.: +91 948 3742561.
E-mail address: abhigos@platinum.materials.iisc.ernet.in (A. Goswami).

http://dx.doi.org/10.1016/j.engfailanal.2014.01.019
1350-6307/Ó 2014 Elsevier Ltd. All rights reserved.
182 A. Goswami, S. Kumar / Engineering Failure Analysis 39 (2014) 181–187

1.1. Effect of adding rare earth elements

The protective oxide layers of chromium and aluminum, which form at high temperatures in these alloys, act as a barrier
between the substrate and the environment thereby reducing further oxidation. But upon exposure to oxidizing atmo-
spheres for extended periods at high temperatures the chromium oxide layer tends to become non-protective in nature.
The internal stresses which increase as the thickness of the oxide layer increases [9] and the formation of volatile CrO3 at
high temperatures leads to the formation of internal cracks and decreased oxide scale adhesion. An improvement in this
has been achieved by the addition of rare earths in the alloy. These can be (1) pre-alloyed with the base metals, or (2) alloyed
with the anti-coking films that are applied on the internal surface of the furnace coils [10,11].
The rare earth ions present in the anti-coking film diffuse towards the base alloy and contribute in forming a diffusion
barrier. The mechanism most widely accepted attributes the improvements to segregation–diffusion of the rare earth ions
to oxide grain boundaries [12]. The oxygen potential gradient, which extends from the gas interface into the substrate, sets
up the path for the diffusion of the RE ions, which first segregate to the metal-scale interface and then diffuse inwards into
the scale. The RE ions follows the fastest path to the gas interface i.e. the scale grain boundaries. The ionic radii of the rare
earths are significantly higher than that of the elements in Fe–Cr–Ni alloys, and their presence at the alloy or oxide grain
boundary impedes cation diffusion. This in turn transforms regular anion diffusion into the predominant diffusing species
and thus determines oxide growth [13–17].
Introducing very low amounts (0.1%) of rare earth elements to alloys has been proven to be very effective in improving
the reliability of the oxide scale. Although the action of rare earth elements is not fully understood, several mechanisms have
been proposed [18], including but not limited to the following:

 Improving the scale adhesion through the development of oxide pegs into the alloy acting as mechanical keying agents.
 Reducing the accumulation of voids at the alloy/scale interface leading to better adhesion.
 Imparting higher spallation resistance by enhancing the scale plasticity through the modification of the oxide structure.

The outward cationic diffusion, which has been observed in Fe–Cr–Ni alloys, generates vacancies that, upon accumula-
tion, may lead to the formation of voids at the alloy/oxide interface (lack of adhesion) and eventually spallation [18]. How-
ever, the formation of the voids could be prevented by adding rare earth elements like Y, Ce or Sc, that are believed to act as a
sink for the vacancies.

2. Investigation

The radiant coil assembly of the ethylene furnace investigated at Reliance Industries petrochemical complex (Gujarat, In-
dia) is as shown in the figure and consists of four passes (W-shaped, Fig. 1) in which all the passes are made up of 35% Cr–45%
Ni alloy. The coils were internally coated with an anti-coking film to increase decoking time by reducing coke formation.
During operation a leak was detected in a second pass tube and the furnace was taken off the service for detailed inspection
and repairs.
The leak from the coil was observed in the form of a crack which had opened up to one-third of its circumference (see
Fig. 2a). The region surrounding the crack appeared blistered (see Fig. 2b) and recorded high magnetic permeability values.
Further investigation revealed similar blisters at six different locations with each of them being located on the inlet pass of
the furnace coil assembly. Visually these blisters appeared similar to the blister in the cracked tube except for the fact that
these had not yet cracked completely.

3. Experimental results

The failed coil samples were subjected to various non-destructive testing and microstructural analysis.

3.1. Macrostructural examination

The macrostructural examination reveals that the damage is highly localized in nature and the affected region had taken
the form of a blister (see Fig. 3a and b).
The depth of the blistered region is comparable to the thickness of the radiant tube. The nature of attack seems to be
external and slightly greenish layers formed in the blistered region suggest the presence of oxides of chromium. It appeared
as if the outer surface of the tube had undergone oxidation and due to poor oxidation resistance the subsequent layers were
oxidized as well.

3.2. Liquid penetrant testing

The liquid penetrant test revealed the presence of cracks in all the cases (see Fig. 4a and b). Coil samples in which the
cracks were observed on both the inner and outer surfaces reflect a higher extent of oxidation damage in such a way that
 A. Goswami, S. Kumar / Engineering Failure Analysis 39 (2014) 181–187 183

Fig. 1. Coil assembly in an ethylene cracking furnace.

Fig. 2. (a) Opening at a failed location; (b) local blisters on the coil.

Fig. 3. Cross sectional view of the radiant tube showing through thickness damage due to severe oxidation.

the entire thickness of the furnace coil had been affected. Samples in which the cracks observed were only on the outer
surface indicate a relatively lesser oxidative damage.
184 A. Goswami, S. Kumar / Engineering Failure Analysis 39 (2014) 181–187

Fig. 4. (a) Inner side of the radiant tube showing the damaged location; (b) dye penetrant test performed on the inner side confirm the presence of cracks on
the internal surface of the tube and hence the severity of oxidation assisted cracking which led to the failure.

3.3. Microstructural examination

The unaffected cast microstructure of 35Cr–45Ni alloy has an austenitic matrix with a discontinuous network of inter
dendritic primary precipitates (see Fig. 5a and b) and the hardness was measured to be 254 HV. The blistered region mea-
sured a hardness in the range of 297–322 HV and the microstructure reveals damage in terms of oxide formation and coars-
ened carbide precipitates. The high hardness values in the damaged region can be attributed to the coarsened carbides
formed in the blistered region. The total thickness of the oxide layers was comparable to the thickness of the radiant tube
depicting the high depth of oxidative damage.

3.4. SEM and EDS analysis

The blistered region of the coil was sectioned perpendicular to its axis. EDX analysis was carried out to map the constit-
uent elements in selective areas (see Fig. 6a and b). Following conclusions were drawn based upon the results:

i. The average oxygen percentage was approximately 38%. This high percentage of oxygen accounts for the presence of
oxides of base metals present in the parent alloy.
ii. The average carbon percentage was approximately 7%. This is primarily because of the carbides (mainly of Cr, Fe and
Ni) present in the blistered area. The fissures/defects provide a path for the diffusion of carbon from the carbon rich
environment (cracked gas) to the carbon deficient environment (coil). Carbon diffusion coupled with high temperature
leads to the precipitation and coarsening of carbides.
iii. Localized presence of Cerium (rare earth) in high percentage up to 24% (see Table 1). Cerium was found to be excep-
tionally high in a selective region while no traces of it or any other rare earth were observed at various other locations
randomly analyzed in the blistered region. This suggests a non-homogenous distribution for the rare earths and thus
the oxidation resistance provided by these would be rendered ineffective. The isolated rare earth distribution would
facilitate oxide precipitation leading to internal stresses, increased substrate brittleness and oxidation assisted
cracking.

Fig. 5. Optical micrographs: (a) microstructure of the unaffected (as cast) 35Cr–45Ni alloy showing an austenitic matrix with inter dendritic primary
precipitates; (b) microstructure of the affected region showing coarsened precipitates.
 A. Goswami, S. Kumar / Engineering Failure Analysis 39 (2014) 181–187 185

Fig. 6. SEM micrograph of the oxidized region: (a) micrograph showing the presence an oxidized region towards the outer side of the tube i.e. the side
exposed to the burners in a furnace; (b) the points labeled A, B, C and D correspond to the different spots where EDS measurements.

Table 1
EDS analysis at the blistered region.

Element %Age
Oxygen 37.56
Cerium 23.79
Carbon 7.37
Iron 2.20
Chromium 6.86
nickel 2.20
Other Traces

3.5. Electron Probe Micro Analysis (EPMA)

Electron probe micro analysis was carried out for the oxidized area and the results show a decrease in the elemental con-
centration (measured in ppm) for nickel, chromium and iron as we move from the inner (unaffected) surface to the outer
(oxidized) surface. It also shows an increasing trend in terms of oxygen concentration with a small region of unidentified
material in the middle (Fig. 7b). The cracks in the oxidized region appear to converge at this unidentified region. EDS carried
out at this location confirmed the presence of cerium.

4. Discussion

The radiant coils used in the ethylene cracking furnace are made by centrifugal casting process. In this process, a perma-
nent mould is rotated continuously about its axis at high speeds (300–3000 rpm) as the molten metal is poured. The melt is
centrifugally thrown towards the inside mould wall, where it solidifies after cooling.

Fig. 7. EPMA results (a) backscattered image of the oxidized region revealing the presence of cracks due to embrittlement; (b) elemental mapping for
oxygen showing high concentrations in affected regions.
186 A. Goswami, S. Kumar / Engineering Failure Analysis 39 (2014) 181–187

Fig. 8. Diagrammatic representation of the mechanism proposed for the furnace coil failure showing the innermost coated region of the coil (a) diffusion in
sound alloy; (b) preferential diffusion in alloy with a defect site.

The tendency to induce defects increases with increasing pressure during casting. Use of too high speed of rotation in cen-
trifugal casting is critical [19]. The danger of mould particles breaking off and getting entrained in the melt as it fills the
mould cavity increases with increasing velocity of melt flow, particularly when the flow is turbulent. Thus centrifugal cast-
ings tend to cause more of such defects than static castings. These defects can be in the form of pores which can be empty or
filled with non-metallic inclusions. These defects tend to disturb the homogeneous diffusion of cerium (rare earth) from the
anti-coking film towards the parent alloy which is essential to the formation of an effective diffusion barrier. The presence of
defects act as high energy sites which promote selective diffusion of rare earth ions through the alloy matrix resulting in
their segregation. Presence of defects (e.g. porosity) coupled with the high operating temperature of the furnace tends to
increase the diffusion rate of the rare earth ions. The rare earth metals like Y, Ce and Zr are susceptible to solute segregation
and are also characterized by significant free energy changes for carbide and oxide formation thereby leading to internal
stresses, substrate embrittlement and crack initiation [20]. The region surrounding the segregated region is depleted of
the rare earth ions which in turn makes it less oxidation resistant and promotes further cracking (see Fig. 8a and b).

5. Conclusion

1. The results of the investigation indicate the presence of inherent casting defects which could have been due to the use of
an inferior batch of investment material.
2. The decreased oxidation resistance of the 35Cr–45Ni coil coated with an anti-coking film alloyed with cerium (rare earth)
is due to the solute segregation of cerium ions at the site of casting defect.
3. The results of EDS and EPMA examination gave further evidence of cerium segregation in the parent alloy at the location
of oxidative cracking.

Acknowledgements

The authors would like to thank Reliance Industries Limited for permission to publish the paper.

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